HYDROPROCESSING PILOT PLANTS

Modern petroleum refining Hydroprocessing – the use of hydrogen to convert

operations have to meet tight
crude oil and other feedstocks into higher value
specifications in terms of sul-
fur and nitrogen levels, olefin
products. Pilot plants are used to optimize the
and aromatic content and process and develop/test new catalysts.
heavy metals such as vana-
dium and arsenic. Hydroprocessing

Over the last half century,

a variety of hydroprocess-
ing technologies have been
developed to enable refiners
to meet the continuous tight- Hydrotreating: HT Hydrodewaxing Hydrogenation
ening specifications imposed Hydrodemetallization: HDM
upon the industry. All hydro- Hydrodenitrification: HDN
processing technologies con- Hydrodesulfurization: HDS Hydrofinishing
sume hydrogen and typically
convert heavy oil fractions
Hydrocracking: HC
into lighter and more valuable
products.
HYDROTREATING (HT)

This technology removes undesirable materials from

petroleum feedstocks by selectively reacting these
streams with hydrogen in a catalyst bed at elevated
temperatures and pressures.

Hydrodemetallization Hydrodenitrification Hydrodesulfurization

(HDM): (HDN): (HDS):
This process removes This process catalytically This technology is the most
metals out of petroleum removes nitrogen out of the common hydrotreating reaction.
crudes. Generally, nickel petroleum crude. There are two Sulfur containing hydrocarbons
and vanadium are present in broad categories of nitrogen come in a large variety of forms
crudes that may also contain compounds -- basic nitrogen and the desulfurization ability
silicon, lead and arsenic. associated with six-member rings varies from one feedstock to
These metals are poisonous and neutral nitrogen associated another. For example, straight
for downstream operations with five-member rings. The run naphthas can be almost
and must be removed by inherent complexity of nitrogen completely desulfurized,
hydrocleaving. The cleaved compounds makes denitrification whereas heavier materials
metals are deposited on the a difficult proposition. The such as resids can only be
sacrificial catalysts that must be NH3 that is generated must be desulfurized down to a 50-70%
periodically replaced. subsequently removed. level. Hydrodesulfurization
produces H2S which must be
subsequently removed.

HYDROCRACKING (HC)

Hydrocracking can increase the yield of gasoline presence of hydrogen. The

components and also creates a 25% gain in volume. hydrogen and the catalyst
are complementary in several
Hydrocracking is the most gain in volume. The cracking/ ways. First, the catalyst
severe form of hydrotreating. hydrogenation combination causes cracking which needs
In this process, the feedstock results in products whose heat to keep it going. This
oil flows over a high activity average gravity is lower than the step is an endothermic
catalyst at temperatures >650°F feed. Hydrocracking produces process. On the other hand,
and pressures >1,000 psig. high quality gasoline (jet fuel and as the cracking proceeds, the
diesel fuel) from heavy gas oils. hydrogen saturates (fills out)
Hydrocracking can increase the the molecules – an exothermic
yield of gasoline components Hydrocracking is simple. process that gives off the heat
and also creates a 25% It is cat cracking in the to keep the process going.
Another way in which the Typical hydrogen consumption fractionator is run to cut out
hydrogen and catalyst are is about 2,500 scf/bbl. After the bottoms which are again
complementary has to the hydrocarbon leaves the mixed with the hydrogen
do with the formation of first stage reactor, it is cooled stream and charged into the
isoparaffins. Cracking forms and liquefied and run through second stage reactor. Since
olefins, which can join together a hydrogen separator. The this material has already
to form normal paraffins. hydrogen is recycled into the been subjected to some
Hydrogenation rapidly fills feed. The typical hydrogen hydrogenation, cracking and
out all the double bonds, recycle rate is between 5,000- reforming in the first stage,
thus forming isoparaffins 7,000 scf/bbl. The liquid is the operation of the second
that prevent the reversion to charged into a fractionator. stage is more severe in terms
less desirable molecules -- Depending on the products of higher temperatures and
isoparaffins have higher octane desired (gasoline components, pressures.
numbers than normal paraffins. jet fuel and gas oil), the

Typical examples of hydroprocessing catalysts are shown in the table below.

COMPONENT HYDROTREATING HYDROCRACKING

Active Metal Catalyst MoS2 MoS2 WS2

Pd/Pt
Promoters Ni/Co Ni/Co
γ-alumina
Support Increasing amount
H-Y….ZSM….SAPO zeolites
Acidic Support Increasing amount

HYDRODEWAXING – HYDROFINISHING

Hydrodewaxing These isoparaffins have a high from the feedstock -- typically

viscosity index, low pour points responsible for both the brown
This process involves the fixed and oxidation resistance. color and instability. One route
bed catalytic hydrogenation for hydrofinishing is to use a
of gas oils to produce motor classical desulfurization catalyst
base oils and lubricating oils. Hydrofinishing at low severity operating
One route is to selectively conditions. The other route
hydrocrack the paraffinic (waxy) This process is used to adjust uses noble metal catalysts
components in the feedstock. the color and stability of motor that claim excellent oxidation
The preferred modern option is base oils and lubricating oils. stability and superior color.
to catalytically hydroisomerize The technology completely This option operates at lower
the molecular structure of the removes aromatics, oxygenates pressures and smaller reactor
wax into C20+ isoparaffins. and unsaturated molecules volumes.
 HYDROGENATION Background in Hydroprocessing
• Eight hydrocracker/hydrotreater pilot plants for the Research
Hydrogenation generally defines Institute of Petroleum Processing (RIPP), Sinopec. These
a process in which the feedstock systems are still being operated at the Beijing R&D Center.
is reacted with hydrogen in • Four reactor molten salt based hydrotreater (all four reactors
the presence of a raney nickel, are in the same molten salt bath) that enable high speed
palladium or platinum catalyst. analysis of catalytic performance.
The most common application
• Four independent single reactors in molten salt baths -- four
of this process is to reduce or
independent trains, especially important for maintaining
saturate organic compounds
isothermality in highly exothermic hydrocracking reactions.
such as the hydrogenation
of unsaturated fats to make • Four hydrocracker demonstration plants equipped with
saturated fat products. Most simulated adiabatic electric furnaces.
hydrogenation processes use • Ebulliating bed hydrotreaters for coal hydro liquefaction
gaseous hydrogen, but some and bitumen upgrading -- at pressures up to 5,000 psig.
involve the alternative sources of
• Supercritical water (SC) hydrotreater. This unit used SC
hydrogen – these processes are
water to enhance the kinetics of hydrodesulfurization and
called transfer hydrogenations.
hydrodemetallization.
• Dual reactor multi-zone adiabatic hydroprocessing unit.
• Gradientless Spectrum reactor with a static basket for
hydroprocessing catalyst evaluation.
• Orinoco crude Ore-emulsion hydroprocessing demonstration
plant for demetallization and desulfurization.
• Hydrocracking of heavy tar sands to make lighter feedstocks.
• Ultra-low sulfur diesel (ULSD) demonstration plant.
• Sorbitol hydrocracker for converting sorbitols into polyol
based materials. This technology was the genesis of the new
bio-refining industry that is rapidly emerging in the US.

Two Recent
Hydroprocessing
Units made by Unitel

If you are interested in learning more about Hydroprocessing System

479 Business Center Drive #105
Pilot Plants & Demo Plants, please contact Unitel Technologies:
Mt. Prospect, IL 60056
Tel: 847-297-2265
www.uniteltech.com